Pad bath formulation of iron salt,ammonium oxalate and zirconyl ammonium carbonate

ABSTRACT

ORANGE TO BROWN MINERAL DYEINGS ARE CONVENTIONALLY PREPARED FROM TWO BATH SYSTEMS, WHERE THE FABRIC IS WETTED WITH ONE BATH CONTAINING AN IRON SALT, AND THEN WETTED WITH ANOTHER BATH CONTAINING ALKALI TO CAUSE THE COLORED IRON OXIDE TO DEPOSIT IN THE FABRIC AS A MINERAL DYE. THIS BEEN NECESSARY UP TO NOW SINCE IT HAS BEEN CHEMICALLY INCOMPATIBLE TO HAVE THE IRON IN THE SAME ALKALINE BATH WITH THE ALKALI, THIS INVENTION DEMONSTRATES THAT A HEAT DECOMPOSABLE COMPLEX OF THE IRON, WITH OR WITHOUT MANGANESE, CAN BE COMPATIBLE WITH ALKALINE ZIRCONYL AMMONIUM CARBONATE SOLUTIONS IN THE SAME BATH, WHEN CELLULOSICS CAN BE WETTED IN THIS BATH, AND SUBSEQUENTLY MINERAL DYED BY HEAT CURING, WHEN THE COMPLEX OF IRON DECOMPOSES TO DEPOSIT IRON OXIDE WITH ZIRCONIA, THE ZIRCONYL AMMONIUM CARBONATE DECOMPOSING AT THE SAME TIME TO DEPOSIT ZIRCONIA, WHEN HEPTAVALENT MANGANESE (KMNO4) IS INCORPORATED INTO THE BATH WITH THE COMPLEXED IRON, IT IS SOLUBLE AND COMPATIBLE, PRODUCING MANGANESE DIOXIDE (MNO2) BY REDUCTION PRODUCTS FROM THE IRON COMPLEX, RESULTING IN VARIOUS SHADES OR ORANGE TO BROWN WITH THE IRON OXIDE AND ZICONIA ALSO DEPOSITED. THIS PROCESS MAKES IT POSSIBLE TO DEPOSIT ORANGE TO BROWN WASH-FAST MINERAL DYEINGS FROM A SINGLE BATH, THE DEPOSITIED ZIRCONIA ATTRIBUTES A DEGREE OF WATER REPELENCY AND ALAGAECIDAL RESISTANCE TO THE FABRIC, AND A COPPER OR PHENYL-MERCURY SALT CAN BE INCORPORATED INTO THE ZIRONYL AMMONIUM CARBONATE COMPONENT OF THE SYSTEM TO DEPOSIT A FUNGICIDAL MINERAL DYE OF ORANGE TO BROWN SHADE ON HEAT CURING, MAKING IT POSSIBLE TO APPLY AN IRON AND/ OR MANGANESE MINERAL DYE WITH OR WITHOUT FUNGICIDE FROM A SINGLE BATH, REDUCING CONVENTIONAL DYEING PROCEDURES FROM TWO OR MORE BATHS, TO A SINGLE BATH REQUIRING ONLY A SIMPLE PAD. DRY, AND CURE PROCEDURE TO EFFECT THE DYEING. THE FABRICS ARE NOT SERIOUSLY TENDERED, AND THE RESIDUAL BY-PRODUCT SALTS MAY OR MAY NOT BE REMOVED BY WASHING, SINCE THE FABRIC IS NOT STIFFENED BY THEIR PRESENCE AND THE DYED COLORS ARE UNAFFECTED ON STANDING.

United States Patent 3,702,753 PAD BATH FORMULATION OF IRON SALT,AMMONIUM OXALATE AND ZIRCONYL AMMONIUM CARBONATE Charles J. Conner,Metairie, La., assignor to the United States of America as representedby the Secretary of Agriculture No Drawing. Original application May 19,1970, Ser. No. 38,900, now Patent No. 3,671,178. Divided and thisapplication Mar. 21, 1972, Ser. No. 236,591

Int. Cl. 61/00 US. Cl. 852 3 Claims ABSTRACT OF THE DISCLOSURE Orange tobrown mineral dyeings are conventionally prepared from two bath systems,where the fabric is wetted with one bath containing an iron salt, andthen wetted with another bath containing alkali, to cause the colorediron oxide to deposit in the fabric as a mineral dye. This has beennecessary up to now, since it has been chemically incompatible to havethe iron in the same alkaline bath with the alkali. This inventiondemonstrates that a heat decomposable complex of the iron, with orwithout manganese, can be compatible with alkaline zirconyl ammoniumcarbonate solutions in the same bath, when cellulosics can be wetted inthis bath, and subse quently mineral dyed by heat curing, when thecomplex of iron decomposes to deposit iron oxide with zirconia, thezirconyl ammonium carbonate decomposing at the same time to depositzirconia. When heptavalent manganese (KMnO is incorporated into the bathwith the complexed iron, it is soluble and compatible, producingmanganese dioxide (MnO by reduction products from the iron complex,resulting in various shades or orange to brown with the iron oxide andzirconia also deposited. This process makes it possible to depositorange to brown wash-fast mineral dyeings from a single bath. Thedeposited zirconia attributes a degree of water repellency andalgaecidal resistance to the fabric, and a copper or phenyl-mercury saltcan be incorporated into the zirconyl ammonium carbonate component ofthe system to deposit a fungicidal mineral dye of orange to brown shadeon heat curing, making it possible to apply an iron and/ or manganesemineral dye with or without fungicide from a single bath, reducingconventional dyeing procedures from two or more baths, to a single bathrequiring only a simple pad, dry, and cure procedure to effect thedyeing. The fabrics are not seriously tendered, and the residualby-product salts may or may not be removed by washing, since the fabricis not stiffened by their presence and the dyed colors are unaffected onstanding.

This is a division of application Ser. No. 38,900 filed May '19, 1970,now US. Pat. 3,671,178.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to a process for imparting to cellulosicmaterials an orange to brown mineral dyeing with resistance to Washingand biological degradation. Specifically, this invention relates to aprocess for imparting to cellulosic materials, through a single bathapplication, an orange to brown series of mineral dyed color shades withresistance to actinic degradation with or without resistance tobiological degradation. More specifiaclly, the invention relates to theformation and subsequent in situ deposition of complex mineral depositsderived from iron, manganese, and zirconium, with or without copper 'iceand mercury in cellulosic materials, to produce mineral dyeings andfungicidal mineral dyeings of said cellulosic materials for the purposeof producing new shades of orange to brown mineral dyeings by reducedprocessing procedures, resistant to actinic degradation, water washing,and biological degradation. Among the great number of useful items whichcan be fabricated from the materials treated by the process of thepresent invention are: awnings, tents, tarpaulins, beach umbrellas, shoeliners, life raft covers, sails, cording material, tobacco shade cloth,curtains, camouflage fabrics, etc.

The prior art teaches the application of iron based mineral dyeings bydouble decomposition wherein several baths and washings are commonlyrequired to obtain the desired finish. In addition, the application offungicides required separate pad-dry-cure procedures, separate from themineral dyeings. By the method which is the present invention, arevolutionary chemical mechanism is necessitated wherein a ferric saltis complexed in an aqueous solution of ammonium oxalate and mixed withzirconyl ammonium carbonate aqueous solution, which become compatible,in solution, with soluble ferric salt-ammonium oxalate alkalinecomplexes so produced. Potassium permanganate is also soluble in thismedium (alkaline) without decomposition, making it possible toincorporate variable amounts of manganese with the iron to producevarious shades of orange to brown mineral dyeings on heat decompositionof the bath on cellulosic fabrics. When a phenylmercuric salt (acetate,lactate, propionate) is dissolved in the zirconyl ammonium carbonate,prior to incorpartion into the dye bath, a. fungicidal component isintroduced into the bath, which is deposited with zirconia on heatdecomposition (reference US. Pat. No. 3,291,635).

Particularly attractive colorations in an orange to brown color rangeare obtained in the cellulosic final products of the present invention.Some of these color shades are in a comparable range with commercialshades now on the market. A significant feature of the present inventionis the ability to impart orange to brown iron based mineral dyeings withand without fungicide by in situ deposition from a water soluble singlebath system, by a simple wet pad and dry-cure procedure.

The main object of this invention is to provide a single bath process toimpart color shades of mineral orange to brown, with or withoutfungicide, by means of simple pad and cure procedures.

A second object of this invention is to produce desired color shades oforange to brown by reducing the need for excessive investment inequipment by reducing the stages or the number of baths which have beencommonly employed in the current industrial processing for iron basedorange to brown mineral dyeings.

A third object of this invention is to provide a process which requiresless chemical and processing controls than those now commonly employedin the art.

In general, this present invention can best be described as a processfor imparting to cellulosic textiles a mineral dyeing consisting ofvarious proportions of iron, manganese, and zirconium oxides with andwithout copper and for phenyl-mercury zirconium fungicides, wherein thecombined properties are obtained upon submitting the untreated textileto a single-bath application, comprising:

(a) impregnating a cellulosic textile with a solution containing from 1%to 6% ammonium oxalate and zirconyl ammonium carbonate solution (10% ZrOfrom 10% to 20%, along with 1% to 4% either ferric sulfate [Fe (SO -xHO] or ferric chloride.

(FeCl with or without 0.5% to 3.7% potassium permanganate (KMnO whereall of the lower percentages are formulated together for a minimum, andall of the highest percentages are formulated together for a maximumlevel; or

(b) impregnating a cellulosic textile with a solution containing 1% to6.0% ammonium oxalate and to 16% zirconyl ammonium carbonate solution(10% ZrO with either 0.5% to 3.7% potassium permanganate (KMnO or 1% to4% either ferric chloride (FeCl -6H O) or ferric sulphate where thelowest percentages are formulated together for a minimum range, and themaximum range constitutes formulating with the highest percentages;

(c) impregnating a cellulosic textile with solutions of (a) withoutpermanganate, or (b) without permanganate where the 10% to zirconylammonium carbonate solution (10% ZrO contains from 0.2% to 0.6% mercuryas metal, as represented by phenylmercuric acetate, lactate, orpropionate; or

(d) impregnating a cellulosic textile with solutions of (a) or (b) withor without permanganate, where the 10% to 20% zirconyl ammoniumcarbonate solution (10% ZrO contains from 0.4% to 1.0% copper as metal,as represented by copper metaborate or copper carbonate;

(e) removing the excess solution from the impregnated cellulosicmaterial to obtain about from 50% to 80% wet pickup,

(f) drying the wet, impregnated cellulosic material for about from 4 to8 minutes of time, at temperatures about from 60 C. to 100 C., using thelonger drying times with the lower temperatures, and

(g) curing the dye, impregnated cellulosie material for about from 1minute to 2 minutes at temperatures about from 100 C. to 105 C., usingthe longer curing times with the lower temperatures; or

(h) dry-curing the wetted sample at 100 C. for 6 minues, or 60 C. for 10minutes.

The incompatability of ferric salts with alkali is known in theliterature. Consequently, ferric oxide pigments have been deposited froma two-bath system in conventional iron based mineral dyeings:

Ibath 2nd bath This invention demonstrates a process for application ofiron oxide mineral dyeings from a single complex salt bath system, whichmay be explained by the following equations:

Fc(OH)al 3NaCl 2Fe[(NH4)-C2O4]2 HO-Zr(NH4CO;)3 deep orange solublecomplex When permanganate is incorporated into the formulation, themanganese reduction by theory follows:

QZ Q -H O-MMOHML reddish brown pigment GNHa Consequently, when thepermanganate is mixed with the ferric salt in ammonium oxalate, the K CObyproduct acts as an acid acceptor during the cure, along with zirconiafrom the decomposition of the zirconyl ammonium carbonate.

It should be noted that ammonium salts and complexes with iron areresponsible for inhibited iron hydroxide precipitation in the alkaline(pH 8.5 to 9.0) bath, and that the subsequent heat decomposition of theammonium compounds, with loss of ammonia, activates the reduction ofpermanganate and precipitation of iron (ic) oxide, along with zireonia(ZrO from the decomposition of zirconyl ammonium carbonate. In theformulation of a pad bath with ferric chloride or sulphate, ammoniumoxalate, and zirconyl ammonium carbonate, the iron is held in solutionby water soluble complex formations (brownish-yellow solutions), wherethe pH is as high as 9.0 and well on the alkaline ammoniacal side of thepH scale. Zirconyl ammonium carbonate creates the necessary bathalkalinity, and is compatible in solution with the iron and manganese inthe padding bath. Also, the zirconyl ammonium carbonate solubilizescopper metaborate, copper carbonate, and phenylmercury salts, producingwater soluble complexes, which are compatible with the dye bath wherethe copper-zirconium is compatible with all baths of manganese and/oriron, but the phenylmercuric salt-zirconium is only compatible with themanganese fall iron baths. On heat decomposition, these fungicidesproduce practically insoluble residues with zirconia and the iron and/ormanganese oxides, to produce fungicidal mineral dyeings in cellulosics(US. Pat. #3,291,635).

EXAMPLE 1 Demonstrates the decomposition of potassium permanganate oncellulosics by heat catalysis. The following formulation was prepared:

G. Potassium permanganate (KMnO 1.00 Water (distilled) 31.00

Dye bath for Manganese Brown 32.00

A sample of scoured duck 8" x 9" was wetted with the bath and allowed toair dry at room temperature (25 C.). The purple colored fabric slowlydeposited brown manganese dioxide (hydrated) over a period of 1 hour,and no purple permanganate remained unreduced at that time. A secondsample of scoured duck 8" x 9" was wetted with the bath, blotted free ofexcess liquid, and oven dried at 60 C. for 10 minutes. A completereduction of permanganate resulted in a manganese oxide brown mineraldyeing, demonstrating the complete reduction (chemical) by heatcatalysis. A third sample of duck 8" x 9" was wetted with the bath,blotted free of excess liquid, and oven dried at C. for 6 minutes.Complete reduction to a manganese oxide brown mineral dyeing resulted inall instances. However, the higher temperature cure (100 C.) produced adifference in color shade, being more golden brown than the sample curedat 60 C. This demonstrates one of the component reactions occurring inthe single dye baths where potassium permanganate is one of theingredients.

'EXAMPLE 2 Demonstrates the reaction and effect of depositing manganesebrown mineral dyeings with zirconia (ZrO Potassium permanganate (KMnO1.00

Water (distilled) 26.00 Zirconyl ammonium carbonate solution (10% ZrO5.00

Dye bath for reddish-brown (1% Mn) 32.00

A purple dye bath solution results. A sample of scoured duck 8" x 9" waswetted with the bath, blotted free of excess liquid, and oven dried at60 C. for 10 minutes. A second sample 8" x 9" of duck was wetted,blotted, and oven dry-cured at 100 C. for minutes. A reddishbrownmineral dyeing occurred in both instances, which was an entirelydifferent color shade of brown as obtained with permanganate alone(Example 1).

EXAMPLE 3 Demonstrates accelerated heat decomposition of potassiumpermanganate with ammonium oxalate, where the potassium ion issufiiciently present to react with oxalic acid as byproduct.

G. Potassium permanganate (KMnO 1.00 Ammonium oxalate (NH C O 'H O) 0.50Water (distilled) 30.50

Dye bath for Manganese Brown (1% Mn) 32.00

A clear deep purple dye bath resulted. A sample of scoured duck 8" x 9"was wetted with the bath, blotted free of excess, and oven-dry-cured at100 C. for 6 minutes. A manganese (oxide) brown mineral dyeing resultedwithout severe fabric degradation, as a result of suitable potassiumcontent for the oxalic acid byproduct. Some degradation occurs frompermanganate oxidation.

EXAMPLE 4 Demonstrates fabric degradation or tendering where the oxalicacid exceeds the potassium content of the bath.

G. Potassium permanganate (KMnO 1.00 Ammonium oxalate (NH C O -H O 1.00Water (distilled) 30.00

Dye bath for Manganese Brown 32.00

A clear deep purple dye bath resulted. A sample of scoured duck 8" x 9"was wetted with the bath, blotted free of excess liquid, and ovendry-cured at 100 C. for 6 minutes. A manganese brown mineral dyed fabricresulted. Some fabric degradation was evidenced by hand tearing, andtensile breaking strength was reduced approximately 40%.

EXAMPLE 5 Demonstrates the effect of zirconia deposition with manganeseoxide brown and ammonium oxalate with sufiicient potassium and zirconiafor byproduct oxalic acid.

Potassium permanganate (KMnO 1.00

Ammonium oxalate (NH C O 'H 0 0.50

Water (distilled) 25.50 Zirconyl ammonium carbonate solution (10% ZrO4.00

Dye bath manganese reddish brown 32.00

EXAMPLE 6 Demonstrates an iron oxide orange single bath aqueous complexwith zirconyl ammonium carbonate solution, for

mineral dyeing a bright orange shade of color. The following formulationwas prepared (5993-124-V):

Ferric sulphate (Fe (SO -xH O) 2.00

Ammonium oxalate ((NH C O -H O) 3.00

Water (distilled) 40.00 Zirconyl ammonium carbonate solution (10% ZrO5.00

Bright orange dye bath 50.00

Demonstrates an iron oxide orange single pad bath system of complexediron in aqueous solution with zirconyl ammonium carbonate, using ferricchloride as an iron source (5993124-VII).

G. Ferric chloride (FeCl -6H O) 2.00 Ammonium oxalate ((NH C O -H O)3.00 Water (distilled) 40.00 Zirconyl ammonium carbonate solution (10%ZrO 5.00

Deep bright orange dye bath 50.00

A clear coffee colored bath resulted. A sample of scoured duck 8" x 9"was wetted with the bath, blotted free of excess liquid, and oven curedat C. for 6 minutes. A uniform deep bright orange mineral dyed fabricwas produced. The hand was soft, and no evidence of fabric degradationcould be detected by hand breaking. A section of the cured treatedfabric was hot tap water Washed for 10 minutes at 55 C., followed by anoven drying at 130 C. for 2 minutes. No loss of mineral dye could bedetected, and the bright orange color was uniform and comparable withthe unwashed sample. Hand was as soft as untreated duck.

EXAMPLE 8 Demonstrates a combination of high iron and low manganese inthe same single bath to produce a brownish-orange color shade(5993-125-1V).

A clear deep purplish-brown bath resulted, with both iron and manganesein solution. A section of scoured duck 8" x 9" was wetted with the bath,blotted free of excess liquid, and oven dried at 60 C. for 8 minutes,followed by oven curing at 100 C. for 2 minutes. A brownish-orangemineral dyed fabric was produced, the manganese shading the orange tothe brown side in color. The dyed fabric retained between 89% and 90%retained strength (tensile) and was not adversely affected by hot tapwater washing (55 C.) for 10 minutes, followed by oven drying at C. for3 minutes. Reduction in permanganate reduced 0xidative degradation.

7 EXAMPLE 9 Demonstrates a combination of high manganese and low iron inthe same single bath to produce an orangebrown mineral dyed fabric(5993-l36III).

G. Potassium permanganate (KMnO 1.00 Ferric sulphate (Fe (SO -xH O) 0.25Ammonium oxalate (NI-I C O -H O 0.50

Water (distilled) 43.25

Zirconyl ammonium carbonate solution (10% ZrO 5.00

Orange-brown mineral dye bath 50.00

A clear deep purple bath solution resulted. A section of scoured duck 8"x 9" was wetted with the fath, blotted free free of excess liquid, andoven dry-cured at 100 C. for 6 minutes. An orange-brown mineral dyedfabric resulted. The treated fabric was strong and showed high tensilestrength by hand breaking. The sample was hot tap water washed for 10minutes at 55 C., followed by oven drying at 130 C. for 3 minutes. Themineral dyeing was stable to hot water washing.

EXAMPLE l Demonstrates a combination of equal iron and manganese toproduce tan mineral dyeings from a Single bath (5993-125I).

G. Potassium permanganate (KMnO 0.50 Ferric sulphate (Fe (SO -xH O) 0.50Ammonium oxalate (NH C O -H O 0.50 Water (distilled) 43.50 Zirconylammonium carbonate solution (10% ZrO 5 00 Light tan mineral dye bath50.00

A deep purple colored clear bath resulted. A section of scoured duck 8"x 9" was wetted with the bath, blotted free of excess liquid, and ovendried-cured at 100 C. for 6 minutes. A light tan mineral dyeingresulted.

EXAMPLE. 1 1

Preparation of Stock (A) copper metaborate-zirconyl ammonium carbonateand (B) phenylmercuric acetatezirconyl ammonium carbonate aqueoussolution for mineral dye bath additions:

G. Copper metaborate powder (Shepherd Chem. Co.) 8.00 Zirconyl ammoniumcarbonate solution (10% ZrO 90.00 Ammonium hydroxide (29.5% NH 2.00

Copper metaborate-zirconyl ammonium carbonate 100.00

Stock solution containing 3.2% copper as metal and 9.0% zirconia (ZrOWhen 5 g. (parts) of this stock are formulated into the mineral dyebaths, 0.16 g. of copper and 0.45 g. of ZrO are introduced into the dyebath in solu- Stock solution containing 3.99% mercury as metal and 9.1%zirconia (ZrO When 5 g. (parts) of this stock are formulated into aManganese-free dye bath, 0.199 g. Hg and 0.455 g. of zirconia (ZrO areintroduced into the dye bath in solution.

The copper-zirconium stock (A) was found to be com patible with mineraldye baths containing manganese, iron, and combinations of both.

EXAMPLE l2 Demonstrates fungicidal mineral dyeing a reddish brown withmanganese, copper, and zirconium in a single bath system. Since coppermetaborate-zirconyl ammonium carbonate (A) stock was found to becompletely compatible with manganese-zirconium single bath mineraldyeing systems, in any proportion, the following bath was prepared andapplied to scoured duck:

Potassium permanganate (KMnO 1.00

Water (distilled) 25.50

Ammonium oxalate (NH C O -H O 0.50 Zirconyl ammonium carbonate-Cumetaborate Clear (reddish-brown) purple dye bath 32.00

A clear purple solution of the bath resulted, containing 0.5% copper(Cu) metal with 0.46% zirconium as ZrO A section of scoured duck waswetted with the bath, blotted free of excess liquid, and oven cured atC. for 6 minutes. A deep reddish-brown fungicidal copperzirconia mineraldyed fabric was produced. The dyeing was subjected to 10 minute hot tapwater washing, followed by a quick oven dry at 130 for 3 minutes. Themineral dyeing was stable to hot water washings and no evidence offabric tendering could be detected by hand breaking. Samples of the dyedfabric, before and after water washing, were X-ray fluorescence analyzedfor copper, manganese, and zirconium:

Percent Percent Percent Mn Zr 11 Sample Before Wash 0. 44 3. 03 O. 19After Wash 0. l5 3. 07 0. 15

The fungicidal copper, manganese, zirconium mineral dyemg was stable towashing with hot Water.

EXAMPLE 13 Demonstrates the incorporation of phenylmercuricacetate-Zirconyl ammonium carbonate (B) stock into a manganese-free ironbath for bright Orange mineral dyeing with fungicide.

Bath is orange brown in color and clear. It contains 0.39% mercury asmetal. A section of scoured duck 8" x 9" was wetted with the bath,blotted free of excess liquid, and oven dried at 100 C. for 4 minutes,followed by a cure of C. for 1 minute. A bright orange mineral dyeingresulted, having a fungicidal phenylmercury content. A section of thecured fabric was washed with hot running tap water for minutes, followedby oven drying at 130 C. for 3 minutes. The dyeing was stable to hotwater washing. Mercury analyses before and after wash showed 0.26%before and 0.21% after wash.

EXAMPLE 14 Repetition of Example 13 using ferric chloride FeCl 6H O inplace of ferric sulphate (Fe (SO -xH O). The mineral dyeing was deeperand brighter organge in color shade. The mineral dyeing was stable tohot water washing, and the mercury analyses before and after wash were0.28% and 0.22%.

EXAMPLE Demonstrates the incorporation of the copper metaborate-zirconylammonium carbonate with an iron-ammonium oxalate bath, withoutmanganese, for bright organe copper-based fungicidal mineral dyeingsfrom a A clear coffee brown colored bath solution is produced, and thiscontains 0.32% copper as metal and 0.39% zirconium as ZrO A section ofscoured duck 8" x 9" was wetted with the bath, blotted free of excessliquid, and oven dry-cured at 100 C. for 6 minutes. A bright orange(fungicidal) mineral dyeing resulted, having a theoretical coppercontent of approximately 0.2% (Cu). The dye color shade was comparableto the color shade produced in Example 7, where no fungicide wasincorporated. Tensile breaking strength showed approximately 90%-95%retained strength after treatment. Copper analyses were made before andafter 10 minute hot tap water wash:

Sample: Percent copper (Cu) Before wash 0.17 After wash 0.13

The color shade was also stable to hot tap water washing.

EXAMPLE 16 Demonstrates the acid oxalic tendering effect withpermanganate baths with excess ammonium oxalate.

Bath (A) contains approximately 0.247 g. potassium and 0.63 g. oxalicacid. Bath (B) contains 0.247 g. potassium and 0.315 g. of oxalic acid.When both baths are applied to scoured duck 8" x 9", and both treatedfabrics cured at 130 C./5 minutes, the fabric treated with (A) shows 44%strength loss (tensile strength), while the fabric treated with (B)shows only 29.0 strength loss. Excess oxalic acid increases oxidativedegradation.

EXAMPLE l7 Demonstrates several color shade bath systems, usingmanganese and iron with zirconia:

5993-134-II (manganese-zirconia) G. Potassium permanganate (KMnO 1.00Water (distilled) 26.00 Zirconyl ammonium carbonate (10% ZrO 5.00

Reddish-brown dye bath 1% Mn) 32.00

5993-136-I (manganese-zirconia) G. Potassium permanganate (KMnO 1.00Ammonium oxalate (NH C O 'H 0.25 Water (distilled) 25.75 Zirconylammonium carbonate 10% ZIOZ) 5.00

Reddish-brown dye bath 1% Mn) 32.00

5993-125-1 (manganese, iron, and zirconia) G. Potassium permanganate(KMnO 0.50 Ferric sulphate (Fe (SO -xI-I O) 0.50 Ammonium oxalate (NH CO -H O 0.50 Zirconyl ammonium carbonate (10% ZrO 5.00 Water (distilled)43.50

Orange-brown mineral dye bath (0.35 Mn) 50.00

5993--111 (manganese, iron, and zirconia) G. Potassium permanganate(KMnO 0.50 Ferric sulphate (Fe (SO xH O) 1.00 Ammonium oxalate (NH C O-H O 1.00 Zirconyl ammonium carbonate (10% Zr0 5.00 Water (distilled)42.50

Light brownish orange mineral dye bath (0.35%

Bright orange mineral dye bath (0% Mn) 50.00

5993-124-VI (manganese, iron, and zirconia) Potassium permanganate (KMnO0.50 Ferric sulphate (Fe (SO -xH O) 2.00 Ammonium oxalate (NH C O -H O3.00

Water (distilled) 39.50

Zirconyl ammonium carbonate (10% ZrO 5.00

Medium orange-brown mineral dye bath (0.35%

5993-136III (manganese, iron, and zirconia) Potassium permanganate (KMnO1.00

Ferric sulphate (Fe (SO -xH O) 0.25

Ammonium oxalate (NH C O -H O 0.50

Water (distilled) 43.25

Zirconyl ammonium carbonate (10% ZrO 5.00

Deep orange-brown mineral dye bath (0.7%

5993-137-II (iron and zirconia) Ferric chloride (FeCl -6H O') 2.00

Ammonium oxalate (NH C O -H O 3.00

Water (distilled) 35.00

Zirconyl ammonium carbonate (10% ZrO 10.00

Bright orange (High ZrO mineral dye bath The Zirconyl ammonium carbonate(10% ZrOz) may be increased to 20% of the formulation in any of thepreceding formulations, and is only limited by cost for even higherpercentages to 50% ZrO Higher ZrO concentrations reduce acid fabrictendering, increase the color shade brightness, and add to lightscreening and algaecidal properties.

EXAMPLE 18 Demonstrates the application of the color shade baths ofExample 17 to scoured duck: Each of the nine baths so prepared were usedto wet two 9" x 12" sections of scoured 10 oz. duck. The untreated duckwas thoroughly wetted with the bath, blotted free of excess liquid, andoven dried at 90 C. for minutes, followed by an oven cure of 100 C. for2 minutes, when the respective mineral dye was completely deposited,with the respective color shade being obtained. The cured samples wereallowed to cool under room conditions (25 C.) for one hour. The mineraldyeings were designated as follows:

5993134IIReddish-brown 5 993-1 3 6-I-Reddish-brown5993-125-I-Orange-brown 5993l25IIILight brownish-orange 5993125IVLightorange 5993-124VBright orange 5993124VIMedium orange-brown 5993-136IIIDeep orange-brown 5993-137IIBright orange The color shade range isbetween orange and brown.

EXAMPLE 19 One each of the treated samples prepared in Example 18 weredesignated for washing, and were subjected to a Wash of running hot tapwater (55 C.) for a period of minutes. The washed samples were thenremoved, blotted free of excess water, and oven dried at 130 C. for 3minutes. The color was compared with the unwashed respective samples. Inevery instance, the color was negligibly affected, and the washedcolored fabrics were comparable to the corresponding unwashed coloredfabrics, showing the mineral dyeings to be stable to hot water washing.

EXAMPLE 20 Samples of the mineral dyed fabrics before washing, and thecorresponding mineral dyed fabrics after 10 minutes hot tap waterwashing, were submitted for X-ray fluorescence analyses for manganese,iron, and zirconium percentages:

BEFORE WASHING Percent Percent mangazirco- Sample nese Percent niurnnumber Color shade Mn iron Fe Zr 5993-13441- Reddlsh-brown 0. 49 0. 052. 01 5993-136-1 do O. 51 O. 06 2. 6993-1254 Orange-brown 0. l4 0. 15 2.79 6993--111. Light brownish-orange- 0. 16 0. 28 2. 00 5993125IV. Lightorange 0. 10 0. 35 2. 11 6993-124-V Bright orange 0. 002 0. 66 2. 335993-125-VI.-. Medium orange-brown. 0. 14 0. 56 2. 75 5993-136-III- Deeporange-brown 0. 29 0. 10 2. 81 5993-137-II. Bright orange 0. 003 0. 694. 93

During washing, the color shades are stable and only surface depositswere removed, as evidenced by X-ray fluorescence analyses with thewashed samples:

AFTER WASHING Percent Percent mangazirco- Sample nese Percent niumnumber Color shade Mn iron Fe Zr 5993-125-IW- Orange-brown.-. 0. 14 0.14 2. 50 5993-125-IIIW Light brownish-orange. 0. 12 0. 26 1. 965093125IVW Light orange 0.09 0. 28 1. 69 5993124VW Bright orange 0. 0020. 45 1. 79 5993-124-VIW... Medium orange-brow 0.12 0.49 1. 805993-126-111. Deep orange-brown- 0. 25 0. 08 1. 92 5993137II.... Brightorange 0. 002 0.58 3. 97

The residual manganese, iron, and zirconium add-ons, after washing, arewell above theory for 60% wet pickup, demonstrating good hot water washresistance and retention of mineral dye pigment (color).

EXAMPLE 21 Sections of cured and unwashed mineral dyed scoured ducksamples were tested for tensile breaking strength to determine theeffect of the treatment on the fabric in heat curing. The results arereflected in the following results:

Tensile strength retention was high in all formulations where manganese(permanganate) was less than 0.3% as Mn add-on. The high iron (orange)and less than 0.3% manganese to 0% Mn, orange to brownish-orange shadesof mineral dyed fabrics showed 86% to 99% retained tensile strengthvalues.

EXAMPLE 22 Demonstrates the tendency of permanganate to reduce thefabric strength through oxidation in heat curing without ammoniumoxalate or subsequent oxalic acid degradation. The followingformulations were prepared and applied to scoured duck:

G. Potassium permanganate (KMnO 1.00 Water (distilled) 31.00

Bath for (Basic) Manganese Brown (1% Mn).. 32.00

Two samples of duck were wetted with the bath, blotted free of excessliquid, and cured as follows:

(1) one sample at C./3 minutes followed by 140 C. for 2 minutes. (2) onesample at 100 C./6 minutes (dry-cure).

13 Sample (1) showed a 40% fabric strength (tensile) loss, and sample(2) showed a 40% fabric strength (tensile) loss, showing thatpermanganate alone causes fabric degradation by oxidation in heat curingwithout acid (oxalic). Degradation is relative to the amount ofpermanganate (oxidation) present in the bath, and not temperature.

G. Potassium permanganate (KMnO 1.00 Water (distilled) 26.00 Zirconylammonium carbonate (10% ZrO 5.00

Reddish-brown dye bath (1% Mn) 32.00

Two samples of duck were wetted with the bath, blotted free of excessliquid, and cured as follows:

( 1) one sample at 130 C./3 minutes followed by 140 C. for 2 minutes.(2) one sample at 100 C./6 minutes (dry-cure).

Sample (1) showed a 44% tensile strength loss, and sample (2) showed a47% fabric tensile strength loss, showing that ZrO; does not retardfabric oxidation by the permanganate, and that lowering the curingtemperature does not reduce oxidation tendering with Zr present.Consequently, tinting with permanganate should be regulated to keep themanganese add-ons under 0.3% on the fabric, with or without iron oxidein any concentrations,

since iron oxide deposition from this process does not demonstratesignificant fabric degradation.

I claim:

1. A pad bath formulation, said bath consisting of about up to 4 partsof an iron salt, selected from the group consisting of ferric chlorideand ferric sulphate, about 6 parts of ammonium oxalate, about 80 partswater, and about 10 parts of a zirconyl ammonium carbonate solutioncontaining about 10 weight percent zirconium dioxide.

2. A pad bath formulation prepared according to the process of claim 1wherein the iron salt is ferric chloride.

3. A pad bath formulation prepared according to the process of claim 1wherein the iron salt is ferric sulphate.

References Cited UNITED STATES PATENTS 3,394,027 7/1968 Conner et al117-1385 2,923,592 2/ 1960 Crosland 8-52 3,291,635 12/ 1966 Conner117-143 X 3,431,059 3/1969 Conner et a1. 8-52 3,183,118 5/1965 Connerl17138.5 3,446,656 5/ 1969 Conner 117-1385 GEORGE F. LESMES, PrimaryExaminer P. C. IVES, Assistant Examiner US. Cl. X.R. 117-385; 106-304

